Method and composition for improving gas barrier properties of polymeric containers and films
AssigneeE. I. Du Pont de Nemours and Company
InventorsIrene Greenwald Plotzker, Thomas Michael Ford, Kenneth George Sharp, Samuel Tacitus D'Arcangelis
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Abstract
A polymer composition and method for reducing the permeability of gases through molded polymeric containers and films by incorporating into the polymer from which the container or film is formed an effective amount of a barrier-enhancing additive, such as monoesters of hydroxybenzoic acid and hydroxynaphthoic acid.
Claims20
A method for reducing gas permeability of shaped thermoplastic polymeric articles wherein the polymer from which the article is formed is selected from the group consisting of polyesters, polycarbonates, polyetherimides and polyethersulfones and wherein the method comprises the steps of:
- (1) incorporating into the polymer an amount of a barrier-enhancing additive or a mixture of barrier-enhancing additives effective to reduce gas permeability and selected from the group consisting of:
- (a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
- wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl;
- Ar is substituted or unsubstituted phenylene or naphthylene;
- or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
- (b) diesters of hydroxybenzoic acid of the formula (B)
- wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (BB) where M is as defined above;
- (c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
- wherein R and Ar are as defined above;
- or formula (CC) where M is as defined above;
- (d) diamides of hydroxybenzoic acid of the formula (D)
- wherein Ar is as defined above, and R2 is C1-C4 alkyl (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (DD) where M is as defined above;
- and
- (e) ester-amides of hydroxybenzoic acid of the formula (E)
- where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above by first forming a physical mixture comprising the polymer and one or more of the gas barrier enhancing additives, (2) heating the mixture to a temperature sufficiently high to melt the polymer but low enough to maintain the one or more gas barrier enhancing additives substantially in its or their original molecular form, and (3) forming the article.
A thermoplastic polymer composition comprising (1) a base polymer which is selected from the group consisting of polyesters, polycarbonates, polyetherimides and polyethersulfones, including their homopolymers, random or block copolymers and a blend or blends of such homopolymers and copolymers and (2) an amount of one or more gas barrier-enhancing molecular additives, or a mixture of such gas barrier-enhancing molecular additives, effective to reduce the gas permeability of the base polymer and selected from the group consisting of:
- (a) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
- wherein R and Ar are as defined above;
- or formula (CC) where M is as defined above;
- (b) diamides of hydroxybenzoic acid of the formula (D)
- wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (DD) where M is as defined above;
- and
- (c) ester-amides of hydroxybenzoic acid of the formula (E)
- where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
A thermoplastic polymer composition comprising:
- (1) a base polymer which is a polyester homopolymer or copolymer which contains structural units derived from one or more organic diacids or their corresponding esters selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid and the derivatives thereof which are the dimethyl, diethyl, or dipropyl esters or acid chlorides of the dicarboxylic acids and one or more diols selected from the group consisting of ethylene glycol, 1,3-propane diol, naphthalene glycol, 1,2-propanediol, 1,2-, 1,3-, and 1,4-cyclohexane dimethanol, diethylene glycol, hydroquinone, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, triethylene glycol, resorcinol, and long chain diols and polyols which are the reaction products of diols or polyols with alkylene oxides, and the gas barrier-enhancing molecular additive or mixture of such gas barrier-enhancing molecular additives are present in the polymer composition at a total concentration of from 0.1% by wt. up to about 20% by wt. of the composition;
- and
- (2) an amount of a gas barrier-enhancing molecular additive or mixture of such gas barrier-enhancing molecular additives effective to reduce gas permeability of the base polymer and selected from the group consisting of:
- (a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
- wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl;
- Ar is substituted or unsubstituted phenylene or naphthylene;
- or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
- and
- (b) diesters of hydroxybenzoic acid of the formula (B)
- wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2.where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (BB) where M is as defined above.
A shaped thermoplastic polymeric article comprising a base polymer having physically incorporated therein an amount of one or more barrier-enhancing additives effective to reduce permeability of the shaped article to gases when compared to the shaped article not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
- (a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
- wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl;
- Ar is substituted or unsubstituted phenylene or naphthylene;
- or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
- (b) diesters of hydroxybenzoic acid of the formula (B)
- wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (BB) where M is as defined above;
- (c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
- wherein R and Ar are as defined above;
- or formula (CC) where M is as defined above;
- (d) diamides of hydroxybenzoic acid of the formula (D)
- wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (DD) where M is as defined above;
- and
- (e) ester-amides of hydroxybenzoic acid of the formula (E)
- where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
A blow molded thermoplastic polymeric bottle comprising a base polymer having incorporated therein an amount of one or more barrier-enhancing additives that is effective to reduce permeability of the molded bottle to oxygen and carbon dioxide gases when compared to a molded thermoplastic polymeric bottle not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
- (a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
- wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl;
- Ar is substituted or unsubstituted phenylene or naphthylene;
- or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
- (b) diesters of hydroxybenzoic acid of the formula (B)
- wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (BB) where M is as defined above;
- (c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
- wherein R and Ar are as defined above;
- or formula (CC) where M is as defined above;
- (d) diamides of hydroxybenzoic acid of the formula (D)
- wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (DD) where M is as defined above;
- and
- (e) ester-amides of hydroxybenzoic acid of the formula (E)
- where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
A method for producing a blow molded thermoplastic polymeric bottle comprising a base polymer selected from polyester homopolymers and copolymers having incorporated therein an amount of one or more barrier-enhancing additives that is effective to reduce permeability of the molded thermoplastic polymeric bottle to oxygen and carbon dioxide gases when compared to a molded thermoplastic polymeric bottle not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
- (a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
- wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl;
- Ar is substituted or unsubstituted phenylene or naphthylene;
- or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
- (b) diesters of hydroxybenzoic acid of the formula (B)
- wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (BB) where M is as defined above;
- (c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
- wherein R and Ar are as defined above;
- or formula (CC) where M is as defined above;
- (d) diamides of hydroxybenzoic acid of the formula (D)
- wherein Ar is as defined above;
- and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl;
- or formula (DD) where M is as defined above;
- and
- (e) ester-amides of hydroxybenzoic acid of the formula (E)
- where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above, said method comprising the steps of:
- (i) forming a physical mixture comprising the base polymer and one or more of the gas barrier-enhancing additives;
- (ii) heating and melt blending the mixture to a temperature sufficiently high to melt the base polymer but low enough to maintain the one or more barrier-enhancing additives substantially in its or their original molecular form;
- and
- (iii) injection blow molding the bottle.
Dependencies are inferred from the claim text.